CN103949246B - Preparation method for the platinum catalyst that methanol recapitalization combustor is carrier with porous foam titanium - Google Patents
Preparation method for the platinum catalyst that methanol recapitalization combustor is carrier with porous foam titanium Download PDFInfo
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- CN103949246B CN103949246B CN201410210578.XA CN201410210578A CN103949246B CN 103949246 B CN103949246 B CN 103949246B CN 201410210578 A CN201410210578 A CN 201410210578A CN 103949246 B CN103949246 B CN 103949246B
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Abstract
The preparation method of a kind of platinum catalyst being carrier with porous foam titanium for methanol recapitalization combustor, belongs to proton exchange ceramic membrane fuel cells field. Described method is with porous foam titanium for anode, it is placed in the electrolyte containing aluminate to apply direct current or alternating current and carries out differential arc oxidation process, again the ceramic membrane of generation is carried out high temperature sintering, form membrane of oxide ceramics porous, fine and close, carry out the lift-launch of platinum based catalyst in this, as carrier, form the platinum based catalyst for methanol recapitalization combustor. Compared with existing catalyst manufacture method, the present invention can effectively solve the problem that platinum lift-launch amount is not enough and reactant contact area is less and catalysis is active of current methanol recapitalization combustor, thus being effectively improved battery overall performance.
Description
Technical field
The invention belongs to proton exchange ceramic membrane fuel cells field, the preparation method relating to a kind of platinum based catalyst for methanol recapitalization fuel chambers.
Background technology
Constantly transition and revolution along with energy resource structure, new energy source technology has cleaning due to it, pollute the feature such as little, renewable and increasingly receives the concern of people, and fuel cell technology makes its more advantage in performance and price due to its combination with micromachining technology, therefore become one of focus. DMFC (PEMFC) is as a kind of high-new fuel cell technology, due to its have efficiently, high-energy-density, good portability, fuel price are cheap and are prone to supplement, pollute the advantages such as little, all have wide practical use in MEMS, microrobot, mini-medical apparatus, personal mobile communication equipment. The problem that due to methanol crossover cause open-circuit voltage and electric current density reduce intrinsic for solving DMFC, a kind of novel methanol recapitalization fuel cell arises at the historic moment, its feature is carry out fuel supply with the form of gas reactant after high concentration methanol is restructured as hydrogen, and its key component is reformation reative cell and combustor. Reformer chamber is the place that liquid methanol is restructured as gaseous hydrogen; Combustor provides heat for reforming reaction.
Combustor is as the source of reforming reaction heat, and its performance quality determines the degree that reforming reaction carries out, and also determines the performance of whole battery. Being common redox reaction in combustor, namely hydrogen or methanol aqueous solution and oxygen react under the effect of catalyst, produce Joule heat simultaneously.Combustor catalyst mostly is platinum based catalyst, its catalyst lift-launch situation and catalyst activity are the key factor of conditioned response, only have to meet and require that combustor can provide enough long-term heats to react offer condition for reformer chamber, and existing catalyst carries mode and can not fully meet requirement.
Summary of the invention
The purpose of the present invention aims to provide a kind of platinum catalyst manufacture method being carrier with the porous foam titanium processed based on differential arc oxidization technique, compared with existing catalyst manufacture method, the present invention can effectively solve the problem that platinum lift-launch amount is not enough and reactant contact area is less and catalysis is active of current methanol recapitalization combustor, thus being effectively improved battery overall performance.
It is an object of the invention to be achieved through the following technical solutions:
One, the surface modification treatment of porous foam titanium. First, with porous foam titanium for anode, it is placed in the electrolyte containing aluminate, and passes to direct current or alternating current carries out differential arc oxidation process, form alumina titanate ceramics film on porous foam titanium surface. In above-mentioned electrolyte, electrolytical content is 5 ~ 20g/L, and the process time is 20 ~ 180min, the structure that the alumina titanate ceramics film of formation is inner compact layer, outer layer is loose. Secondly, the aluminium titanates oxide ceramic membrane formed is sintered, makes its decomposition be sintered to the secondary porous oxide ceramic membrane structure being main component with aluminium oxide and titanium oxide. Above-mentioned sintering processes temperature is 600 ~ 1000 DEG C, and the sintering processes time is 10 ~ 120 minutes.
Two, the supporting and structure of platinum based catalyst. With the porous foam titanium after above-mentioned differential arc oxidation and sintering processes for matrix, supporting of platinum based catalyst is carried out: surface-treated porous foam titanium dipping is containing after the solution of Pt ion on its surface, drying and heating makes presoma decompose, and reduces before using, activated catalyst.
Existing oxide ceramic membrane processing method mostly is and forms membrane of oxide ceramics by the mode being dried again at metal base surface immersion oxide colloid, and this kind of mode can cause the phenomenons such as oxide is uneven, ceramic membrane is imperfect. And the membrane of oxide ceramics that the present invention is formed with high temperature sintering technique by differential arc oxidization technique, it is possible to accomplish to cover uniform, fine and close, complete and porous membrane of oxide ceramics and its film constituent, the equal scalable of thickness at difform POROUS TITANIUM matrix. It is used for methanol recapitalization combustor, when using original reactant and reaction principle, two aspects are improved: one, as mentioned above, adopt differential arc oxidization technique and high temperature sintering technique that POROUS TITANIUM is carried out surface modification treatment, the ceramic membrane that forming component thickness is controlled, strengthens reliability and the bond strength of film; They are two years old, by adopting POROUS TITANIUM to cover the structure of porous oxidation ceramic membrane, adopt infusion process to carry platinum based catalyst simultaneously, porous oxidation ceramic membrane carrier is made more to carry catalyst by the capillarity of catalyst in lift-launch process, thus having accomplished the increase of catalyst lift-launch amount when same matrix porosity, increasing the contact area of reactant and catalyst, also strengthening the bond strength of catalyst and carrier simultaneously, thus enhancing the extent of reaction, improve the utilization rate of reactant.
Advantages of the present invention is as follows:
(1) adopt the porous foam titanium of high-specific surface area as matrix skeleton structure, with existing carrier when equal-volume compared with catalyst lift-launch amount significantly improve, the contact area of reactant and catalyst increases, and reacts carry out more complete;
(2) differential arc oxidization technique is adopted to form porous ceramics membrane structure with high temperature sintering technique, increase its surface area further, catalyst wicks into inside porous ceramic film simultaneously, improves the bond strength of catalyst and matrix, further increases reaction efficiency and catalyst stability;
(3) porous ceramic film is covered in Titanium skeleton matrix surface, enhances the corrosion resistance of metal, improves the stability of metallic framework, extends service life;
(4) the lift-launch process of catalyst is simple and convenient, can use infusion process, and finished catalyst also can be used directly to support.
Accompanying drawing explanation
Fig. 1 is chamber structure schematic diagram.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme is further described; but it is not limited thereto; every technical solution of the present invention modified or equivalent replaces, without deviating from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1:
The porous foam titanium cut is placed in electrolysis bath, and using it as anode, electrolysis bath is negative electrode, with the Na of 5 ~ 15g/L3AlO3For electrolyte, with 300 ~ 600V DC voltage, 0.05 ~ 0.30A/cm2Constant current density carry out differential arc oxidation process, the process time is 20 ~ 180 minutes, prepare alumina titanate ceramics film.
Being placed in tube furnace by the porous foam titanium covering aluminium titanates membrane of oxide ceramics generated, carry out high temperature sintering process under 600 ~ 900 DEG C of conditions, the process time is 10 ~ 120 minutes, forms salic and titanium oxide ceramics film.
Porous foam titanium after surface modification treatment is immersed in containing Pt (NH3)4(NO3)2Catalyst precursor solutions in, wherein the concentration of Pt is 0.01 ~ 0.1mol/L. After impregnating 5-30 minute, it is dried, then at N2Calcination processing is carried out under atmosphere, at 400 ~ 800 DEG C. At H before using2(25%, v%) N2In atmosphere, reductase 12 hour at 300 ~ 500 DEG C.
The catalyst carrier that above-mentioned process completes is put into combustor as shown in Figure 1, the operation principle of combustor, as it was previously stated, hydrogen contacts with catalyst and oxygen on porous foam titanium surface simultaneously, occurs oxidation reaction to generate water, release substantial amounts of heat simultaneously, supply reforming reaction. Combustor shown in Fig. 1 is the groove being consistent with carrier bulk, and left side is air inlet, is used for inputting methanol aqueous solution or H2And air; Right side is steam vent, is used for discharging reaction product and unreacted reactant.
Embodiment 2:
This example and embodiment 1 are distinctive in that, in described electrolyte containing 10g/L Na3AlO3, DC voltage is 500V, electric current density is 0.10A/cm2, the process time be 60 minutes.
Embodiment 3:
This example and embodiment 1 are distinctive in that, adopting alternating voltage that porous foam titanium is carried out differential arc oxidation process, treatment conditions are: forward voltage is 300 ~ 700V, negative voltage to be 0 ~ 200V, operating frequency be 10 ~ 3000Hz, dutycycle are 10 ~ 60%, the process time is 20 ~ 180min.
Embodiment 4:
This example and embodiment 3 are distinctive in that, forward current density is 10A/cm2, negative current density be 10A/cm2, operating frequency is 500Hz, dutycycle is 30%, the process time is 100min.
Embodiment 5:
This example and embodiment 3 are distinctive in that, forward current density is 15A/cm2, negative current density be 15A/cm2, operating frequency is 1000Hz, dutycycle is 50%, the process time is 60min.
Embodiment 6:
This example and embodiment 1 are distinctive in that, when high temperature sintering processes, fixed temperature is 900 DEG C and carries out Isothermal sinter process.
Claims (9)
1. the preparation method of the platinum catalyst that a kind is carrier for methanol recapitalization combustor with porous foam titanium, it is characterised in that described method step is as follows:
One, with porous foam titanium for anode, it is placed in the electrolyte containing aluminate, applies direct current or alternating voltage carries out differential arc oxidation and processes 20 ~ 180 minutes, form the porous oxide ceramic membrane being main component with aluminium titanates on its surface;
Two, porous oxide ceramic membrane is carried out high temperature sintering process, obtain the titanium foam being coated with aluminium oxide and titanium oxide ceramics film;
Three, to be coated with the titanium foam of aluminium oxide and titanium oxide ceramics film as substrate, carry out supporting of platinum catalyst on its surface, obtain the platinum catalyst for methanol recapitalization combustor.
2. the preparation method of the platinum catalyst being carrier with porous foam titanium for methanol recapitalization combustor according to claim 1, it is characterised in that in described electrolyte, the content of aluminate is 5-20g/L.
3. the preparation method of the platinum catalyst being carrier with porous foam titanium for methanol recapitalization combustor according to claim 1, it is characterized in that applying DC voltage and carry out differential arc oxidation when processing, DC voltage is 300V ~ 600V, electric current density is 0.05 ~ 0.30A/cm2, the process time be 20 ~ 180 minutes.
4. the preparation method of the platinum catalyst being carrier with porous foam titanium for methanol recapitalization combustor according to claim 1, it is characterized in that applying alternating voltage and carry out differential arc oxidation when processing, forward voltage is 300 ~ 700V, negative voltage to be 0 ~ 200V, operating frequency be 10 ~ 3000Hz, dutycycle are 10 ~ 60%, the process time is 20 ~ 180min.
5. the preparation method of the platinum catalyst being carrier with porous foam titanium for methanol recapitalization combustor according to claim 1, it is characterised in that when carrying out high temperature sintering process, its treatment temperature is 600 ~ 1000 DEG C, and the process time is 10 ~ 120 minutes.
6. the preparation method of the platinum catalyst being carrier with porous foam titanium for methanol recapitalization combustor according to claim 1, it is characterised in that the loading method of described platinum based catalyst is infusion process.
7. the preparation method of the platinum catalyst being carrier with porous foam titanium for methanol recapitalization combustor according to claim 6, it is characterized in that concretely comprising the following steps of described infusion process: will be covered with after the titanium foam of aluminium oxide and titanium oxide ceramics film impregnates in the catalyst based presoma of Pt, drying and heating makes presoma decompose, reduce before using, activated catalyst.
8. the preparation method of the platinum catalyst being carrier with porous foam titanium for methanol recapitalization combustor according to claim 7, it is characterised in that the catalyst based presoma of described Pt is Pt (NH3)4(NO3)2Solution.
9. the preparation method of the platinum catalyst being carrier with porous foam titanium for methanol recapitalization combustor according to claim 8, it is characterised in that described Pt (NH3)4(NO3)2In solution, the concentration of Pt is 0.01 ~ 0.1mol/L.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7067453B1 (en) * | 2001-07-13 | 2006-06-27 | Innovatek, Inc. | Hydrocarbon fuel reforming catalyst and use thereof |
| CN101185891A (en) * | 2007-11-29 | 2008-05-28 | 申靓博 | Porous carbon supported platinum-cerium oxide catalyst for fuel cell and preparation thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7067453B1 (en) * | 2001-07-13 | 2006-06-27 | Innovatek, Inc. | Hydrocarbon fuel reforming catalyst and use thereof |
| CN101185891A (en) * | 2007-11-29 | 2008-05-28 | 申靓博 | Porous carbon supported platinum-cerium oxide catalyst for fuel cell and preparation thereof |
Non-Patent Citations (2)
| Title |
|---|
| Characterization and property of microarc oxidation coatings on open-cell aluminum foams;JiaanLiu，et al;《J.Coat.Technol.Res.》;20121231;第9卷(第3期);第357页右栏第2段，第358页实验部分第2段，结论部分 * |
| Effect of alloy on micro-structured reactors for methanol steam reforming;F. J. Echave，et al;《Catalysis Today》;20130413;第213卷;第145页右栏，第146页2实验部分 * |
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Inventor after: Zhang Xuelin Inventor after: Zhang Yufeng Inventor after: Chen Hailong Inventor after: Liu Xiaowei Inventor before: Zhang Xuelin Inventor before: Ma Zezhong Inventor before: Liu Xiaowei Inventor before: Zhang Yufeng |
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Free format text: CORRECT: INVENTOR; FROM: ZHANG XUELIN MA ZEZHONG LIU XIAOWEI ZHANG YUFENG TO: ZHANG XUELIN ZHANG YUFENG CHEN HAILONG LIU XIAOWEI |
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